• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文学位 >Novel synthetic method for N-heterocyclic carbene transition metal complexes and new green catalytic applications.
【24h】

Novel synthetic method for N-heterocyclic carbene transition metal complexes and new green catalytic applications.

机译：N-杂环卡宾过渡金属配合物的新型合成方法和新的绿色催化应用。

获取原文
获取原文并翻译 | 示例
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

The development of safer, more atom economical catalytic reactions and catalyst syntheses is an important goal of green chemistry. In Chapter 2, a novel approach for the green and efficient synthesis of transition metal N-heterocyclic carbene complexes from N,N'-disubstituted imidazolium carboxylates via release of CO2 is presented. This method efficiently affords previously reported and novel NHC complexes of Rh, Ir, Ru, Pt and Pd and avoids the use of strong bases. Tuning the reaction conditions for NHC transfer can give selectively either mono- or bis-NHCs, or bis- and tris-NHC metal complexes. Computational studies elucidate the mechanism of the reaction forming from N,N'-disubstituted imidazolium carboxylates from with (MeO)2CO and N-methylimidazole, and also the NEC transfer step to the metal precursor. The concept of loss of CO2 led in Chapter 3 to the exploration of decarboxylative coupling strategies for making biaryls from benzylic acids and either aryl halides via C-X activation, or unactivated aromatics by C-H activation. We show that microwave heating improves the efficiency of this reaction, and allows the use of benzoic acids which were previously considered to be underactive for decarboxylation. In Chapter 4, a novel iridium-catalyzed C-H activation and functionalization of simple arenes affords aldehydes, esters, and imines in the presence of Ag2CO3 as base and oxidant. A catalytic reaction capable of selective partial reduction of quinoline derivatives using phenyl silane as the reductant is shown to obliterate the need for stoichiometric lithium reagents, which were previously known as the only synthetic route to these compounds. Finally, in Chapter 5, a catalytic strategy for synthesizing amides, functional groups which are typically prepared using toxic stoichiometric reagents, such as thionyl chloride, is presented. It utilizes amines and aldehydes, which when condensed to imines, can oxidized catalytically to oxaziridines. The oxaziridines are and in turn rearranged catalytically to afford the amide.
机译：开发更安全，更经济的原子催化反应和催化剂合成是绿色化学的重要目标。在第二章中，提出了一种新颖的方法，该方法可通过释放CO2由N，N'-二取代的咪唑鎓羧酸酯绿色有效地合成过渡金属N-杂环卡宾配合物。该方法有效地提供了先前报道的新颖的Rh，Ir，Ru，Pt和Pd NHC复合物，并且避免了使用强碱。调整用于NHC转移的反应条件可以选择性地生成单-或双-NHC，或双-和三-NHC金属络合物。计算研究阐明了由N，N'-二取代的咪唑鎓盐与（MeO）2CO和N-甲基咪唑形成羧酸的反应机理，以及NEC转移至金属前体的步骤。减少CO2的概念在第3章中探讨了脱羧偶联策略，该方法用于通过C-X活化由苄酸和卤代芳烃或通过C-H活化未活化的芳烃制备联芳基。我们表明微波加热提高了该反应的效率，并允许使用以前被认为对脱羧反应活性不足的苯甲酸。在第4章中，在Ag2CO3作为碱和氧化剂的存在下，新颖的铱催化的C-H活化和简单的芳烃官能化提供了醛，酯和亚胺。已表明能够使用苯基硅烷作为还原剂选择性地还原喹啉衍生物的催化反应消除了对化学计量的锂试剂的需求，化学试剂锂试剂以前被认为是合成这些化合物的唯一途径。最后，在第5章中，提出了一种合成酰胺的催化策略，酰胺是通常使用有毒化学计量试剂（如亚硫酰氯）制备的官能团。它利用胺和醛，当缩合为亚胺时，可以催化氧化为恶唑烷。恶唑烷并进而催化重排以提供酰胺。

著录项

  • 作者

    Voutchkova, Adelina.;

  • 作者单位

    Yale University.;

  • 授予单位 Yale University.;
  • 学科 Chemistry Inorganic.
  • 学位 Ph.D.
  • 年度 2009
  • 页码 137 p.
  • 总页数 137
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 无机化学;
  • 关键词

  • 入库时间 2022-08-17 11:38:26

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号